Deammoniative Condensation of Primary Allylic Amines with Nonallylic Amines

Abstract

AbstractAn unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through CN bond cleavage. In the presence of 5 mol% palladium diacetate, 10 mol% 1,4‐bis(diphenylphosphino)butane (dppb), and 5 mol% p‐toluenesulfonic acid (TsOH), a range of α‐unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α‐selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity. Replacing dppb with racemic 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) permitted the deammoniative condensation of enantioenriched α‐chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration. Electrospray ionization (ESI) mass spectrometric analysis of the reaction mixture permitted the identification of some π‐allylpalladium intermediates, and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction.